Production of low pour point gas oil and high octane number gasoline

ABSTRACT

A process for the simultaneous dewaxing of high pour point gas oil and upgrading of an aromatic containing naphtha by contact of a mixture of the gas oil and naphtha with a high silica to alumina ratio synthetic aluminosilicate zeolite catalyst, which is derived from a zeolite which was synthesized with an organic cation, incorporating a hydrogenation dehydrogenation component, and a hydrogen atmosphere at about 500* to 1,000*F followed by distillation of the product in order to recover a lower pour point gas oil fraction and a higher octane gasoline fraction.

United States Patent Garwood et al.

PRODUCTION OF LOW POUR POINT GAS OIL AND HIGH OCTANE NUMBER GASOLINE Inventors: William Everett Garwood,

Haddonfield, N.J.; John J. Wise,

Media, Pa.

Assignee: Mobil Oil Corporation, New York,

Filed: Mar. 21, 1974 Appl. No.: 453,246

Related US. Application Data Continuation-impart of Ser, No. 391,380, Aug. 24, 1973.

US. Cl. 208/111; 208/138; 208/141; 260/671 R Int. Cl. ClOG 13/02; C07C 3/52 Field of Search 208/111, 15, 102, 82, 264, 208/299; 260/671 R References Cited UNITED STATES PATENTS 8/1971 Frilette et al. 260/666 [451 July 8, 1975 3,700,585 10/1972 Chen et al. 208/111 3,729,409 4/1973 Chen 208/135 3,753,891 871973 Graven et al. 208/62 3,758,402 9/1973 Oleck et a1. 208/1 11 3,767,568 10/1973 Chen 208/134 3,804,746 4/1974 Chu 203/1 1 1 Primary Examiner-Delbert E. Gantz Assistant ExaminerG. E. Schmitkons Attorney, Agent, or Firm-Charles A. Huggett; Michael G. Gilman [5 7] ABSTRACT 11-Claims, No Drawings PRODL'CTION OF LOW POUR POINT GAS OIL AND HIGH vOCTANE NUMBER GASOLINE This is a continuation in part ofApplication Ser. No. 391,380 filed Aug. 24, 1973.

This invention relates to .petroleum processing. It more particularly refers to the upgrading of various petroleum fractions.

Light gas oil, particularly the 330F and heavier fractions find particular use as jet fuel, Diesel fuel and home heating oil. In at least some locations, there is a specification with respect to maximum pour point (temperature) of these distillate fuels which many light gas oils cannot meet. As a result, the gas oil is down graded to lower value use such as residual fuel.

There has recently been developed a process referred to as catalytic hydrodewaxing in which the gas oil is contacted with hydrogen and a shape selective catalyst adapted to selectively crack or hydrocrack the paraffinic molecules in the gas oil. Initially the catalysts used were those zeolite cracking catalysts which had pore openings sized so that they would admit and crack only normal paraffins and exclude all othergasoil components e.g., e rionite type zeolite. Later this process was improved through substituting Z SM-S type of zeolite for the previouslyused erionite type cracking catalyst.

(See U.S. Pat. No. 3,700,585 Using this type catalyst permitted more efficient operation. In addition to the normal paraffins, paraffms with slight branching e.g., with a methyl side group, were also cracked whereby dewaxing was carried out to a greater extent This permitted lowering of the gas oil pour point in a very efficient manner. The product of hydrodewaxing gas oil is suitably fractionated to produce high yields of dewaxed gas oil boiling in the same range as the feed, some naphtha and some light (Cf) ends.

There is a recently discovered process whereby naphtha contain-ing aromatics, particularly reformate,,can be upgraded from an octane point of view. This process contacts reformate with a ZSM-5 type of zeolite at about 500 to l,00 0F and space velocitiesof up to about WI-ISV whereby some of the normal and singly branched (methyl branched) paraffins are cracked to provide rela'tively small fragments which a lkylatefaromatic rings present in the reformate'lfeed. Thisfco n-v verts very low octane material, i. e., paraff ns to high octane material, aromatics, by alkylat ion. Efficiencies in this process are rather high with exce lle'nt yiel'ds. (See U.S. Pat. No. 3,729,409 The product produced by this process is fractionated to recover high yieldsof higher octane naphthaas well as some light ends.

The catalyst referred to herein is inclusive of a family of high silica to alumina ratio crystalline aluminosilicate molecular sieve zeolites havingan organic cation as produced. These zeolites are known to catalyze the It is an object of this invention to provide a novel process for-carrying out catalytic hydrodewaxing and reformate. upgrading in a more efficient manner.

ing a gasoline boiling rang e petroleum fraction such as naphtha, or reformate containing at least about 20 weight percent aromatics and gas, oil having a pour point of at least about +20F into a feed having a cumulative boiling range in the range'of about C to 850F or anypart thereof; contacting such feed with an organic cation derived, high silica to alumina ratio, crystalline aluminosilicate zeolite at a temperature of about 500 to 1,000F, a space velocity of about 0.5 to 20, a

pressure of about 1 to atmospheres, and a hydrogen to hydrocarbon ratio of about l to 20 to 1; and resolving the product thus formed into a gasoline boiling range (e.g. C to about 400F) fraction having a higher octanenumber than the corresponding boiling range fed, a gas oil fraction having aboil ing range higher than said gasoline (e.g., about 400F.+) and having a lower pour point than the gas oil fed, and a minor C light gas fraction. 1 V

Exemplary'of the .catalystswhich are useful for this process and which fall within the scope expressed hereinabove are ZSM-5 typezeolites, ZSM-l2, ZSM-2 land TEA mordenite. ZSM-12 is described in West German Offenlagenschrifft 2,213,109 and U.S. Pat. No. 3,832,449, ZSM-Zlis described in US Pat. Application Ser. No. 358,192 filed May 7, 1973. TEA mordenite is described in U.S. Patent Application Ser. No.

130,442, filed Apr. 1 1, 1971. All of these references are incorporated herein by reference.

It has been stated, as a step in the described process, that a gasoline boiling range fraction and a gas oil fraction are mixed as a first step. Since most virgin gasoline fractions do not have sufficient aromatic's content to meet the minimum specified herein, this admixture step contemplates a prior refinery operation, such as reforming, in which the aromatics concentration is increased followed by admixture with gas oil. It is to be understood, however, that a separate admixing step is not per se an absolute requirement of this process. It is contemplated that a petroleum cut encompassing both naphtha and gas oil boiling range materials can be taken from appropriate crude sources containing the required'minimum aromatics proportion in the gasoline boiling range fraction and this wide cut fraction processed as further set forth herein. The mixing step should be considered as a requirement that mixed gasoline and gas oil be processed but not necessarily that separate-fractions thereof be separately mixed.

under equivalent conditions operating the two processes individually. This is so even if the processes are separately operated and their products combined for a single product resolution operation.

The catalyst can be used in a fixed, moving or fluid- 5 ized bed as desired with the reaction zone appropriately designed therefor. The reaction zone may be 0perated in an upflow or downflow manner utilizing either trickle or flooded operation. The catalyst can be used as such or can be employed in a matrix as per the referred to patents and applications. It is preferred to provide a hydrogenation/dehydrogenation component, such as nickel or other metals having such known activity, in combination with the zeolite catalyst. In addition, the catalyst may be sulfided in known manner.

The zeolite catalyst of this invention should have a silica to alumina ratio of at least about 12 to l, preferably at least about 60 to 1. It may be used alone or in admixture with a matrixing material such as alumina or silica or the like. When used in a matrix, the proportion of active zeolite material is preferably at least about weight percent. 1

It should be noted that invention is not here claimed in any single or group of catalysts pre se, nor in either the hydrodewaxing or the gasoline upgraded processes individually. Rather, invention is here claimed in the combination process described particularly with respect to its unexpectedly improved yield results.

This invention will be illustrated by the following Examples which are not to be considered to, be limiting on the scope hereof. Parts and percentages are by weight unless expressly stated to be to the contrary.

EXAMPLE 1 Equal volumes of a Libyan high pour (+80F) gas oil and a midcontinent C light reformate were blended, properties of the two materials as follows:

Libyan Gas Oil CJ Light Refonnate 155 168 172 l8l l92 206 223 Gravity, APl 36.6

p 0.8468 ASTM Distillation, "F

IBP 368 579 629 666 685 722 782 Pour Point, Octane No.,

4 The R+O and R+3 octane numbers of the C -390F gasoline were 90.3 and 100.7, respectively (compared to 76.0 and 92.1 for the reformate charge), and the pour point of the 390" gas oil was -'75F (compared to +80F for the gas oil charge).

EXAMPLE 2 The Libyan gas oil set forth in Example 1 alone was passed over a fresh portion of the same catalyst used in Example 1 at 400 psig, 1.0 LHSV, 2500 SCF hydrogen/bbl, 600F, for 27 hours. These conditions were chosen so as to produce a gas oil product having about the same pour point as the gas oil product in Example 1. Yields as follows:

C,+C wt. 7: 0.5 C wt. 7: 7.9 C-L06 n. roll-7r I C 's, vol. 2.9 C -390F gasoline, vol.% 120 390"] Gas oil, vol.% 58.8

The 390F+ gas oil again had a pour point of F, but the R+0 and R+3 octanes of the C -3 90F gasoline were about and 93.8, respectively, much lower than the octane numbers in Example 1.

EXAMPLE 3 The midcontinent light reformate of Example 1 was contacted with the same catalyst at 600F, 3.7 LHSV, 5000 SCF hydrogen/bbl, and 500 psig, sufficient conditions to produce a C -390F product having an octane number R+O of 90.3. Yields as follows:

In one aspect of this invention a mixture of benzene or'aromatics containing gasoline boiling range material such as reformate is mixed with a high boiling range material having a lubricating oil fraction therein such as Foots oil and the mixture subjected to hydrodewaxing as set forth herein. To convert the mixture to a relatively high octane gasoline boiling range product, a dewaxed fuel oil product and a purified lube oil fraction boiling in the range of about 650F+.

EXAMPLE 4 Foots oil having the following properties:

Specific Gravity at 70C 0.8266 Kinematic Viscosity at 2lOF, cs 4.06 Boiling Range, F. approx. 700-900 was mixed with 10% (based upon the total composition) benzene and the mixture treated at 750 psig, 750F, 2 to 0.5 LHSV and 2000 SCF l-l/bbl for l 1 days. The catalyst was ZSM-5 containing 0.47 wt. zinc admixed with a 35% alumina binder. The product was composed of some light gas; a significant naphtha fraction, a fuel oil fraction boiling in the range of about 390 to 650F and a 650F lube oil fraction. The lube oil fraction averaged about 30 vol. of the charge and had the following properties: i

The naphtha fraction boiling in the range of 125 to 390F had the following composition:

Paraffins. Wt. '71 Naphthenes Olefins lndanes & Tetralins Naphthalenes Alkybenzenes Benzene Toluene C Alkyhenzenes C Alkybenzenes Cm Alkybenzenes C Alkybenzenes C Alkybenzenes Total while the fuel oil boiling in the range of 390 to 650F had the following properties;

Gravity. APl 26.3 Gravity. Specific 0.8967 Pour Point. F --65 Aniline No.. "F 70.0 Diesel Index 18.4

What is claimed is: l. A process of upgrading petroleum fractions which comprises contacting an admixture, containing at least 10% benzene, of gasoline boiling range fraction having a boiling range of at least about C to 239F which contains at least about 20 weight percent aromatics and a gas oil fraction having an end point up to about 850F and a pour point of at least about +20F with a catalyst comprising a zeolite consisting essentially of a synthetic crystalline aluminosilicate zeolite derived in an organic cation containing form, having a silica to alumina ratio of at least about 12 to 1 and having a hydrogenation/- dehydrogenation component; converting said admixture in the presence of hydrogen at a space velocity of about 0.5 to 20 WHSV, at a temperature of about 500 to l,000F and at a hydrogen to hydrocarbon ratio of about 1 to 20 to l to a product comprising a gas oil fraction having a lower pour point, a gasoline fraction having a higher octane and a light gas fraction; and resolving said product into said gas oil fraction, said gasoline fraction and said light gas fraction.

2. A process as claimed in claim 1 wherein said gasoline boiling range fraction is reformate.

3. A process as claimed in claim 1 wherein said gas oil fraction has an end point of about 850F.

4. A process as claimed in claim 1 wherein said gas oil fraction has a pour point of about to F.

5. A process as claimed in claim 1 wherein said catalyst comprises a ZSM-5 type zeolite.

6. A process as claimed in claim 1 operated at a pressure of about 1 to 70 atmospheres.

7. A process as claimed in claim 1 wherein said admixture is a wide cut petroleum fraction having a boiling range in the range of about C to 850F.

8. A process as claimed in claim 7 wherein said admixture is a virgin petroleum fraction.

9. A process as claimed in claim 2 wherein said gas oil is a virgin petroleum fraction having a boiling range up to about 850F.

10. A process as claimed in claim 1 wherein said gas oil is a lubricant containing material and wherein said product is resolved to additionally contain a purified lube oil fraction boiling in the range of 650F+.

11. A process as claimed in claim 10 wherein said lube oil containing fraction is Foots oil and wherein the gasoline boiling range fraction comprises benzene.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT N0. 3,893,906 DATED y 975 INVENTOWS) 1 WILLIAM EVERETT GARWOOD and JOHN J. WISE It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 2Q pre se" should read "per sevol Signed and Scaled this twentye h D 8) Of January 1 9 76 [SEAL] A ttes t:

C. MARSHALL DANN C 0 m m issioner ofParents and Trademarks RUTH C. MASON Arresting Officer 

1. A PROCESS OF UPGRADING PETROLEUM FRACTIONS WHICH COMPRISES CONTACTING AN ADMIXTURE, CONTAINING AT LEAST 10% BENZENE, OF GASOLINE BOILING RANGE FRACTION HAVING A BOILING RANGE OF AT LEAST ABOUT C6 TO 239*C WHICH CONTAINS AT LEAST ABOUT 20 WEIGHT PERCENT AROMATICS AND A GAS OIL FRACTION HAVING AN END POINT UP TO ABOUT 850*F AND A POUR POINT OF AT LEAST ABOUT +20*F WITH A CATALYST COMPRISING A ZEOLITE CONSISTING ESSENTIALLY OF A SYNTHETIC CRYSTALLINE ALUMINOSILICATE ZEOLITE DERIVED IN AN ORGANIC CATION CONTAINING FORM, HAVING A SILICA TO ALUMINA RATIO OF AT LEAST ABOUT 12 TO 1 AND HAVING A HYDROGENATION/DEHYDROGENATION COMPONENT, CONVERTING SAID ADMIXTURE IN THE PRESENCE OF HYDROGEN AT A SPACE VELOCITY OF ABOUT 0.5 TO 20 WHSV, AT A TEMPERATURE OF ABOUT 500* TO 1,000*F AND AT A HYDROGEN TO HYDROCARBON RATIO OF ABOUT 1 TO 20 TO 1 TO A PRODUCT COMPRISING A GAS OIL FRACTION HAVING A LOWER POUR POINT, A GASOLINE FRACTION HAVING A HIGHER OCTANE AND A LIGHT GAS FRACTION, AND RESOLVING SAID PRODUCT INTO SAID GAS OIL FRACTION, SAID GASOLINE FRACTION AND SAID LIGHT GAS FRACTION.
 2. A process as claimed in claim 1 wherein said gasoline boiling range fraction is reformate.
 3. A process as claimed in claim 1 wherein said gas oil fraction has an end point of about 850*F.
 4. A process as claimed in claim 1 wherein said gas oil fraction has a pour point of about 80* to 100*F.
 5. A process as claimed in claim 1 wherein said catalyst comprises a ZSM-5 type zeolite.
 6. A process as claimed in claim 1 operated at a pressure of about 1 to 70 atmospheres.
 7. A process as claimed in claim 1 wherein said admixture is a wide cut petroleum fraction having a boiling range in the range of about C5 to 850*F.
 8. A process as claimed in claim 7 wherein said admixture is a virgin petroleum fraction.
 9. A process as claimed in claim 2 wherein said gas oil is a virgin petroleum fraction having a boiling range up to about 850*F.
 10. A process as claimed in claim 1 wherein said gas oil is a lubricant containing material and wherein said product is resolved to additionally contain a purified lube oil fraction boiling in the range of 650*F+.
 11. A process as claimed in claim 10 wherein said lube oil containing fraction is Foot''s oil and wherein the gasoline boiling range fraction comprises benzene. 